Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/32—Alkali metal silicates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O

Definitions

• the invention relates to a poorly soluble alkali silicate, a process for its manufacture and its use in detergents and cleaning agents.
• Crystalline layered sodium silicates (layered silicates) of the formula NaMSi x O 2x + 1 . yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 have been found to be suitable substitutes for the detergent builders phosphate and zeolite proved.
• M sodium or hydrogen
• x is a number from 1.9 to 4
• y is a number from 0 to 20 and preferred values for x 2, 3 or 4
• the use of such crystalline layered silicates for softening water is described, for example, in EP-A-0 164 514.
• Detergent builders perform a variety of functions. Among them are special the removal or reduction of water hardness in the wash tap water used and the supply of alkalinity, i.e. regulation and increase the pH in the wash liquor.
• the aforementioned inorganic incrustations consist of in the form of Calcium carbonate precipitated water hardness or dissolved from deposited residues Detergent builder shares.
• the desired increase in pH in the Washing solution has the result that any dirt particles present a get higher surface charge and so easier to wash from the fabric are remove.
• a poorly soluble alkali silicate of the type mentioned at the outset characterized in that it contains alkali layer silicates in finely divided form in a non-layer silicate alkali silicate environment of the formula x M I 2 O.y SiO 2 , in which M I is an alkali metal and y / x (1.9 to 500): 1 means contains. It is essential that the alkali layer silicates are embedded in a non-layer silicate matrix.
• Y / x (2.0 to 200) preferably means 1.
• M I is preferably sodium.
• the non-phyllosilicate alkali silicate environment from non-phyllosilicate is preferred Composed of sodium silicates.
• non-layer silicate sodium silicates include in particular those amorphous sodium silicates, which are typical in the X-ray powder diffractogram no sharp reflections that can be assigned to an ordered crystal structure, demonstrate; they also have no defined stoichiometric composition.
• the alkali layer silicate made of layered crystalline is preferred Disodium disilicate composed.
• the latter in turn usually consist of at least one polymorphic Phase.
• the sparingly soluble alkali silicate preferably contains up to 10% by weight, based on the alkali silicate content of other components.
• the further constituents are preferably cationic and / or anionic components.
• the cationic constituents are preferably alkali metal ions and / or alkaline earth metal cations and / or Fe, W, Mo, Ta, Pb, Al, Zn, Ti, V, Cr, Mn, Co and / or Ni.
• the anionic constituents are preferably sulfates, fluorides, Chlorides, bromides, iodides, carbonates, hydrogen carbonates, nitrates, oxide hydrates, Phosphates and / or borates.
• the sparingly soluble alkali silicate preferably contains up to 10 mol% boron, based on the total SiO 2 content.
• the sparingly soluble alkali silicate preferably contains up to 50 mol% of phosphorus, based on the total SiO 2 content.
• the sparingly soluble alkali silicate preferably has a medium powder Particle diameter from 0.1 to 150 microns.
• the sparingly soluble alkali silicate preferably has a compacted granulate average particle diameter of 10 to 2000 microns.
• the present object is also achieved by a process for the preparation of poorly soluble alkali silicates, characterized in that a starting material containing sodium silicate is mixed with one or more compounds which contain the components M I , M II and / or Z and brought to crystallization.
• M I means an alkali metal
• M II an alkaline earth metal
• X an element of the third main group
• Z an element of the fifth main group of the periodic table.
• the oxides are preferably suitable as compounds, but other compounds are also suitable.
• the mixing ratio of the reactants is preferably selected so that the mixture has a composition which corresponds to the composition of the alkali silicates according to the invention described above.
• Water glass is preferably used as the starting material containing sodium silicate.
• Silicate sources mixed, spray dried and brought to crystallization.
• the crystallization temperature is preferably 700 to 1300 K.
• the crystallization temperature is preferably 800 to 1200 K.
• the crystallization temperature is particularly preferably 900 to 1100 K.
• the invention also relates to the use of poorly soluble alkali silicate for Manufacture of detergents and cleaning agents, including dishwashing detergents.
• the invention also relates to detergents and cleaning agents, which a contain poorly soluble alkali silicate according to the invention.
• the preferred range in the above detergents and cleaning agents for the Poorly soluble alkali silicate is between 1 to 50% by weight and is particularly preferred between 3 to 30% by weight. According to other embodiments of the invention also contents from 60 to 98% by weight and especially from 70 to 98% by weight prefers.
• washing and and cleaning agents are 1 to 50% by weight and 1 to 30% by weight for the cobuilders; for the pH regulators also 1 to 50% by weight and 1 to 30% by weight for which surfactants 1 to 30 wt .-% and 1 to 20 wt .-% and for that Bleaching system 1 to 40 wt .-% and 1 to 20 wt .-%.
• the cobuilders are preferably crystalline aluminosilicates, mono-, oligomeric or polymeric carboxylic acids, alkali carbonates, alkali ortho-, pyro-, polyphosphate, crystalline alkali silicates with a crystal lattice without layer structure and / or amorphous alkali silicates.
• the bleaching system is preferably active chlorine and / or Active oxygen carrier, bleach activator, catalyst, for removing discoloration usable enzymes, perborate and / or percarbonate.
• the surface-active substances are preferably anionic, cationic, non-ionic and / or zwitterionic surfactants.
• the pH regulators are preferably soda, citric acid, Sodium citrate and / or bicarbonate.
• the reaction with sand can be hydrothermal, that is to say in an aqueous solution at an elevated rate Pressure and temperature or thermal (furnace) by melting or Tempering the reactants with each other ..
• a molar ratio of SiO 2 to Na 2 O of 1.9 ⁇ e ⁇ 4 is set in the aforementioned water glass and then the starting product thus obtained is treated with heat.
• the starting product can be modified before the heat treatment:
• One embodiment is that in hydrothermal process solution in to convert the solid form and / or the water content of the solid form change.
• the water content can be determined by spraying with water (e.g. in one Lödige, Telschig or Schugi mixers) or by drying (e.g. Belt dryer, fluidized bed dryer, flight layer dryer).
• Another embodiment is that which arises in the thermal process Solid to convert into the liquid form and / or the water content in the optimally adjust liquid solution by evaporation or dilution.
• Another embodiment is that which arises in the thermal process Add solid with water and add heat treatment.
• the heat treatment is crucial for layered silicate silica environments.
• Preferred apparatuses are: Rotary tubes, fluidized bed furnaces, mold furnaces, belt furnaces, flue dust furnaces, Muffle furnace used.
• the heat input into the material can be direct, indirect, convective, radiation or contact heated.
• the other ingredients can be at any stage before or after Crystallization are added.
• the further constituents are preferred Implementation with the sand add.
• the further one is particularly preferred Dose ingredients into the solution from the reaction with the sand.
• preference is given to the further constituents in the course of atomizing the solution Add spray drying to the same solution.
• the product after the heat treatment can preferably be physically changed become.
• the grain size is optimal through grinding and subsequent classification set.
• For screening e.g. Allgaier, Rhewum, Locker sieves are used.
• the granulation is preferred by granulation and subsequent classification optimally set.
• the ground powder is placed on a pelletizing plate or added to a mixer with a granulating aid.
• Shear forces agglomerate the material.
• One embodiment is the material to dry subsequently.
• Another embodiment is the material leave undried.
• Granulation aids can be: bentonites, hectorites, saponites, modified or unmodified celluloses, polymers and copolymers, water glass, surfactants and other detergent ingredients.
• the grain size is preferably optimally adjusted by roll compaction, grinding and subsequent classification.
• the ground powder is optionally mixed with an auxiliary and compacted in a roll compactor (Hosokawa-Bepex, Alexanderwerk).
• the pressure is between 2 and 100kN / cm 2 roller width.
• the material can optionally be subsequently dried.
• Compacting aids can be: bentonite, hectorite, saponite, modified or unmodified celluloses, polymers and copolymers, water glass, surfactants and other detergent ingredients.
• the particularly fine distribution can be achieved according to the invention by adjusting the M I 2 O / SiO 2 ratio of the material in the starting product and then causing the alkali layer silicates - the sodium layer silicates being preferred - to crystallize.
• the other constituents are preferably not in the layered silicate part but in the non-silicatic part.
• the poorly soluble alkali silicates according to the invention can - as stated above - Use in detergents and cleaning agents. Are preferred here powder detergent, color and special detergent. Heavy duty detergents are balanced formulations with the aim of achieving the highest possible washing effect.
• Color detergents should above all protect color textiles with regard to fading and Wash out the colors and felt the fibers. Special detergents target narrow application areas such as stain salts, bleach boosters, curtain detergents, Wool detergent etc.
• Builder silicates can continue to be used in water softeners prior to especially in regions with high water hardness, a performance-enhancing effect on the Washing result and a protective effect with regard to the washing machine.
• Detergents and cleaning agents in their form as detergents, water softeners and Machine dishwashing detergents can be in powder, granule and tablet form be used.
• the detergent formulation is for the tablet form mixed and pressed into the appropriate shape with a tablet press.
• the shape can be cylindrical or cuboid or possibly also largely take any other geometric shapes. In the case of the cylindrical shape can the ratio of radius to height is between 0.25 and 4.
• the pressure can be between 12 and 0.3 kN / cm 2 . This is essentially independent of the geometrical shape of the tablet. Multistage pressing is also preferred. Any portion of the formulation is pressed one after the other in several steps, so that several layers result. In the case of a two-layer tablet, a volume ratio of the two layers of 1 to 10 to 10 to 1 is particularly preferred.
• the size of particles in aqueous dispersion is determined with the aid of a Granulometer Microtrac ASVR / FRA from Leeds u. Northrup determined.
• the reflection or diffraction of a laser beam is measured when penetrating the dispersion.
• 400ml of ethanol are pumped through the laser measuring cell.
• the solid sample eg 70 mg
• the particle size distribution is determined after 10 min.
• the evaluation unit of the device calculates the average particle diameter (d 50 value).
• the inserts with the desired sieves are inserted into a Retsch sieving machine.
• the mesh size of the sieves decreases from top to bottom.
• 50 g of the sample material to be examined are placed on the widest sieve.
• the sample material is conveyed through the various sieves by the oscillating movement of the sieving machine.
• the residues on the sieves are weighed and calculated based on the weight of the material.
• the d 50 value can be calculated from the values.
• a mixture of a buffer stock solution and deionized water are added submitted to an ErWeKa disolution tester, stirred and heated to 30 ° C.
• the Buffer stock solution is an aqueous solution of glycine, sodium chloride, Calcium chloride and sodium hydroxide in suitable concentrations.
• the Calcium-sensitive electrode model 932001 from Orion is added to the solution immersed and by replenishing the solution with a calcium stock solution calibrated. This is done with the evaluation unit EA 940 from Orion. After If added, the solution contains a water hardness of 17 ° dH.
• the Orion EA 940 is started simultaneously with the addition of the test substance (1 g).
• the pH of the measuring solution is 10.2.
• the Orion EA 940 indicates the concentration of free calcium ions at certain intervals. With the aid of the previously determined amount of calcium, the amount of bound calcium, ie the calcium binding capacity, is deduced from the concentration of the free, unbound calcium ions after 10 minutes. This is given in mg CaCO 3 / g.
• a sample of the test material is pulverized in a mortar and measured in a Philips PW1710 X-ray powder diffractometer (parameters: Cu K alpha 2 radiation, wavelength 1.54439 Angstroms, acceleration voltage 35 kV, heating current 28 mA, monochromator, scanning speed 3 degrees 2 theta per minute).
• the intensities obtained are evaluated as follows. substance Characteristic peak (d value in angstroms) source Alpha phase 3.29 +/- 0.07, typically 3.31 SKS-5 (EP 0 164 552) hkl 140 from JCPDS No. 22-1397 (but also 19-1233, 19-1234, 19-1237) Beta phase 2.97 +/- 0.06 SKS-7 (EP 0 164 552) hkl 400 from JCPDS No. 29-1261 (but also 19-1236, 23-0529) Delta phase 3.97 +/- 0.08 SKS-6 (EP 0 164 552) hkl 120 from JCPDS No. 22-1396
• the JCPDS numbers refer to reference diffractograms of substances listed by the Joint Committee of Powder Diffraction Standards.
• the optical brighteners are mixed in a quarter of the amount of alkyl ethoxylate and mixed in the household multimixer (from Braun) with half the amount of soda.
• the Lödige ploughshare mixer the rest of the soda and the total quantities Zeolite and polymer for 15 minutes at 300 rpm. mixed. Then half of the remaining nonionic sprayed on in 5 minutes. Then it becomes difficult to dissolve Alkali silicate added and mixed for 10 minutes. Then the rest of the second Half of alkyl ethoxylate (AE) sprayed on for a further 5 minutes.
• AE alkyl ethoxylate
• Brightener added and 10 minutes at 300 rpm. mixed. The mixture is in the tumble mixer from the Lödige mixer under low shear stress with perborate, TAED and Enzymes added and mixed for 15 minutes.
• Test fabrics were used to determine the inorganic incrustation, this is a Cotton terry (from Vossen), each a double-rib cotton, polyester / cotton blend (Type 20A) and standard cotton fabric (Type 10A) the Fa. Laundry research Krefeld Testgewebe GmbH and a Standard cotton fabric from the Federal Materials Testing Institute St. Gallen, Switzerland repeatedly (15 times) washed according to the above procedure. To 15 washes were sampled from each of the tissues and these in a muffle furnace at a temperature of 1000 ° C and a period of 24 hours ashes. The weights of the residues are calculated on the used Fabric quantities (weights) related.
• test detergent a test ultracompact heavy-duty detergent with 30.0% commercially available zeolite manufactured.
• the regulation was adapted to the extent that the optical brighteners in a quarter of the alkyl ethoxylate (AE) and a third of the Soda amount to be mixed.
• the rest of the soda, the polymer and all of it Zeolite is mixed in the Lödige mixer and the rest AE is sprayed on. After that all other components except enzymes, TAED and perborate mixed in. These are then in the tumble mixer under the Lödigemischer prepared mixture mixed.
• test detergent a test ultracompact heavy-duty detergent with 10.0% of the silicate from Example 4 manufactured.
• the provision has been adapted so that the rest of the soda, the Polymer and all of the zeolite are mixed in the Lödige mixer, then the Half of the remaining AE is sprayed on, then the silicate from Example 4 is mixed in and finally the rest of AE is sprayed on.
• test detergent a test ultracompact heavy-duty detergent with 10.0% of the silicate from Example 7 manufactured.
• the provision has been adapted so that the rest of the soda, the Polymer and all of the zeolite are mixed in the Lödige mixer, then the Half of the remaining AE is sprayed on, then the silicate from Example 7 is mixed in and finally the rest of AE is sprayed on.
• test detergent a test ultracompact heavy-duty detergent with 10.0% of the silicate from Example 8 manufactured.
• the provision has been adapted so that the rest of the soda, the Polymer and all of the zeolite are mixed in the Lödige mixer, then the Half of the remaining AE is sprayed on, then the silicate from Example 8 is mixed in and finally the rest of AE is sprayed on.
• test detergent a test ultracompact heavy-duty detergent with 10.0% of the silicate from Example 9 manufactured.
• the provision has been adapted so that the rest of the soda, the Polymer and all of the zeolite are mixed in the Lödige mixer, then the Half of the remaining AE is sprayed on, then the silicate from Example 9 is mixed in and finally the rest of AE is sprayed on.
• test detergent a test ultracompact heavy-duty detergent with 30.0% of the silicate from Example 9 manufactured.
• the regulation was adapted to the extent that the optical brighteners in a quarter of the alkyl ethoxylate (AE) and a third of the Amount of sulfate can be mixed.
• the rest sulfate and the total amount of silicate from Example 9 are mixed in the Lödige mixer and the rest AE is sprayed on. After that, all other components except enzymes, TAED and percarbonate mixed in. These are then in the tumble mixer under the Lödigemischer prepared mixture mixed.
• test detergent a test ultracompact heavy-duty detergent with 47% of the silicate from Example 4 manufactured.
• the regulation was adapted to the extent that the optical brighteners in a quarter of the alkyl ethoxylate (AE) and two thirds of the Bicarbonate amount can be mixed.
• the rest bicarbonate and the total amount of the silicate from Example 4 are mixed in the Lödige mixer and the rest AE sprayed on. After that, all other components except Enzyme, TAED and Percarbonate mixed in. These are then in the tumble mixer under the Lödigemischer prepared mixture mixed.
• test detergent produced a test normal detergent with 10% of the silicate from Example 7.
• the regulation was adapted to the extent that the optical brighteners in the Total amount of alkyl ethoxylate (AE) mixed with a third of Amount of sulfate can be mixed.
• the rest sulfate, the phosphate and the The total amount of the silicate from Example 7 is mixed in the Lödige mixer. After that, all other components except enzymes and perborate mixed in. These are then in the tumble mixer under the Lödigemischer prepared mixture mixed.
• test detergent produced a test normal detergent with 10% of the silicate from Example 9.
• the regulation was adapted to the extent that the entire zeolite, the polymer and the Bicarbonate are mixed in the Lödige mixer, then the first half of the AE sprayed on and then the silicate from Example 9 and the sulfate mixed in and the remaining AE is sprayed on at the end. After that, everyone components other than the enzymes mixed in. These will be afterwards in the tumble mixer with the mixture made in the Lödige mixer.
• test detergent produced a test water softener with 15% of the silicate from Example 8.
• the Regulation was adapted to the extent that the entire zeolite, the polymer, the Bicarbonate, the citric acid, the sulfate and the silicate from Example 8 in Lödigemischer be mixed and then the AE is sprayed on. After that the remaining components are mixed in.
• test detergent a test ultracompact heavy-duty detergent with 15% of the silicate from Example 9 manufactured.
• the provision has been adapted so that the rest of the soda, the Polymer and all of the zeolite are mixed in the Lödige mixer, then the Half of the remaining AE is sprayed on, then the silicate from Example 9 is mixed in and finally the rest of AE is sprayed on.
• everyone other components apart from enzymes, TAED and perborate. This are then made in the tumble mixer below that produced in the Lödige mixer Mix in. With a hydraulic two-column press from Matra, Frankfurt (type 200kN / 4625.00000.
• a machine dishwashing gel is made by using a disperser (Ultraturrax, from Hanke and Kunkel) water glass, phosphate, soda, sodium hydroxide, Phosphonate, polymer, alkanesulfonate, phosphoric acid ester mixed in. Silicate and Finally, sodium hypochlorite is briefly mixed in.
• a disperser Ultraturrax, from Hanke and Kunkel

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• Organic Chemistry (AREA)
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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
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• 1999
  • 1999-09-11 DE DE19943551A patent/DE19943551A1/de not_active Withdrawn
• 2000
  • 2000-09-01 EP EP00118945A patent/EP1083148B1/fr not_active Expired - Lifetime
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